Ryle and Intentionality

After some opening comments on how I think one should approach the philosophy of mind, I look at what relatively little Gilbert Ryle had to say explicitly about intentionality, that occurring almost exclusively in his several papers on phenomenology. Then, I discuss the notion of intentionality with respect to the doctrines of The Concept of Mind, although neither the word nor the idea, strictly speaking, appears anywhere in the book. Following more exposition of my own views, including an argument I have made for a certain specific theory of intentionality, I close with some reflections on Ryle as a modern-day Aristotelian.     

Chemo‐ and Stereoselective Iron‐Catalyzed Hydrosilylation of Ketones

The reduction of ketones with polymethylhydrosiloxane (PMHS) gives the corresponding alcohols in good to excellent yield applying iron‐based catalyst systems. In the case of prochiral ketones, the use of Fe(OAc)₂/(S,S)‐Me‐DuPhos leads to high enantioselectivity up to 99 % ee. The reaction proceeds in the presence of several functional groups such as esters, halides as well as conjugated double bonds, with high chemoselectivity. The advantage of this protocol is that the reaction requires no activating agents or additives.     

Harmonization of methods for analysis of cholesterol oxides in foods--the first portion of a long road toward standardization: interlaboratory study

A compilation of literature data on the content of cholesterol oxidation products (COP) in various food products and in blood demonstrates a large variation in content in products or tissues of very similar nature when analyzed in different laboratories according to a large number of methods. The lack of validated, internationally recognized methodology with published accuracy and precision has so far hindered such assessments. Hence an interlaboratory comparision of methodologies of COP analysis was undertaken on egg yolk powders (EYP), whole milk powders (WMP), skim milk powders (SMP), and lard (L). Each product type had one fresh sample (low) and one aged (high) in COP contents. A total of 17 sets of results on WMP, 15 on SMP and EYP, and 13 on L were compared. Overall results (mg/kg sample) varied extensively: Fresh EYP 0.72-265, aged EYP 2.51-361; fresh WMP 0.02-18.1, aged WMP 0.02-26.9; fresh SMP 0.02-6.51, aged SMP <0.01-6.51; fresh L 0.18-97, aged L 4.15-452. Some results were questioned, viz., those from laboratories not indicating substantial differences between samples "low" and "high" in total COP. Others were excluded because of lack of verification of identity of gas chromatographic peaks by mass spectrometry. Then a more narrow range of core results (mg/kg sample) was observed: Fresh EYP 5.69-29.5 sample, aged EYP 11.8-79.0; fresh WMP 0.12-1.76, aged WMP 1.17-13.7; fresh SMP <0.30-<1.21, aged SMP 0.30-2.26; fresh L 0.18-5.07, aged L 94.4-231. At a workshop discussing the results, numerous recommendations were made toward more reliable methodology for determination of COP in foods.     

Docking of Atomic Clusters Through Nonlinear Optimization

The problem of molecular docking is defined as that of finding a minimum energy configuration of a pair of molecular structures (usually consisting of proteins, DNA or RNA fragments). It is often assumed that the two interacting structures can be considered as rigid bodies and that it is of interest to researchers to develop methods which enable to discover the potential binding sites. Many different models have been proposed in the literature for the definition of the potential energy between two molecular structures, most of which contain at least a term (known as Van Der Waals interaction) which accounts for pairwise attraction between atoms, a repulsion term and a term which takes into account electrostatic forces (Coulomb interaction). Some well known models, and in particular those used in rigid docking, are based on the assumption that the only terms which are relevant in the process of docking are pairwise interactions between atoms belonging to the two different parts of the structure. In this paper the problem of finding the lowest energy configuration of a pair of biomolecular structures, considered as rigid bodies, is defined and formulated as a global optimization problem. In terms of dimension of the search space this formulation is not 'high-dimensional', as there are only six degrees of freedom: 3 translation and 3 rotation parameters. However the energy surface of the docking problem is characterized by a huge number of local minima; moreover each function evaluation is quite expensive (interesting structures usually possess a few thousand atoms each). So there is a strong need both of local and of global optimization procedures. In this paper a local optimization technique, based upon standard non linear programming software and a penalized objective function, is introduced and its potential usefulness in the context of global optimization is outlined.     

Zinc-catalyzed chemoselective reduction of tertiary and secondary amides to amines

General and convenient procedures for the catalytic hydrosilylation of secondary and tertiary amides under mild conditions have been developed. In the presence of inexpensive zinc catalysts, tertiary amides are easily reduced by applying monosilanes. Key to success for the reduction of the secondary amides is the use of zinc triflate and disilanes with dual Si-H moieties. The presented hydrosilylations proceed with excellent chemoselectivity in the presence of sensitive ester, nitro, azo, nitrile, olefins, and other functional groups, thus making the method attractive for organic synthesis.